Treatment of oxygen derivatives of hydrocarbons in which aliphatic hydrocarbons predominate



Patented June 29, 1937 UNITED STATES PATENT oFricE TREATMENT OF OXYGENDERIVATI'VES or HYDROCARBONS IN WHICH surname HYDROCARBONS PREDOMINATE Joseph Hidy James. Pittsburgh, Pa, assignor to Clarence P. Byrnes, trustee, Sewickley, Pa.

No Drawing.

16 Claims.

In various copending applications, including my application Serial No. 435,355, filed January 6, 1921, I have disclosed partial oxidation processes for the treatment of mineral oils, including petroleum, shale oil and theoil or tar produced by thelow temperature distillation of coal. In such method, the oil or fraction thereof is vaporized, mixed with air, and the mixture passed at a regulated temperature below a red heat in con-' tact with a catalyst, such. as the oxides or compounds of molybdenum, vanadium, etc. The condensedproducts of this partial oxidation process extend from-alcohols throughaldehydes, to aldehyde fatty acids, all of varying molecular weights, depending upon the fraction employed for the I process.

My present invention relates to the treatment of such mixturescontaining oxygen derivatives of hydrocarbons in which aliphatic hydrocarbons predominate, in the range from alcohols to acids which, according to the present invention, I fractionally distill preferably by a vacuum process into separate fractions. I have found that where careful fractionation is employed, there is a gradation in properties of both the saponiflable' and non-saponiflable portions of each fraction of the product treated, in passing from the fraction of lowest average molecular weight to that of highest average molecular weight, which it is possible to vaporize under the best distillation means. Steam is preferably employed in connection with this vacuum distillation, as'it'aids in vaporization and also serves to hydrolize the wax-like bodies and anhydrides that are present.. The vacuum distillation was employed in order to vaporize each fraction at the lowest possible uct mixture showed the following:

, distillation.

Application March 26, 1924, Serial No. 702,136

oil charged. The specific gravity of densed product was .892 at F.

The Engler distillation on the oxidation prod-.

the con- Per cent I 5 by volume Under 200 C 15 200 to 250 C.. 30 250 to 300 C- 20 m 300 to 350 C 15 x 350 to 400 C.. 10 Residue- 10 Thisproduct was then subjected to a vacuum steam distillation carried-out on several liters u of the product, the various cuts being taken at approximately the volumes above shown. In the further description, I shall refer to each of the portions by its atmospheric pressure distillation range, it being understood that the particular :0

fraction discussed was not separated by atmospheric pressure distillation, but that a cut corresponding to this distillation was made by taking the same percentage volume in the vacuum steam Procedure with the under 200 C. fraction (method A) This portion was boiled under an inverted condenser with a 20% solution of caustic soda for seven hours. The volume offraction taken was 500 cc. and the volume of 20% caustic was cc.

On cooling, a solid cake of soap separated, this being a mixture of sodium soaps of the resinifled aldehyde acids of this fraction. These resin acids 86 were then liberated from the soap by adding a slight excess of dilute sulphuric acid. The resin acids thus liberated were of ,a brickred color, completely soluble in alcohol and in benzol, and

without further purification, showed a softening point of C. and were completely melted at Withthe resins of this and of all other fractions, I discovered that if they are washed with certain solvents; such as petroleum, ether or gas- 45 oline, I can wash out a small amount of oil and softer acids, thus raising both the softening and the melting points of the resins and also improving the colors-of the remaining resin acids. This is'an important feature of my invention, as it 50 may be applied to any and all such resins and will greatly improve them, both by raising the melting point and improving them in color.

The non-saponifiable portion of this fraction is amenable to the ordinary decoloring and deodorizing processes known to industrial chemists. For example, when this portion or fraction is subjected to the ordinary sulphuric acid and caustic soda agitations and to subsequent re-distillation, a product is obtained which is almost water white in color and has a pleasant ethereal odor. This product is suitable for a solvent, for motor fuel, or for a thinner or turpentine substitute in'the paint and varnish industry.

In certain cases in the latter industry, the purification treatment need not be resorted to, as there is sufficient concentration of aldehydes, ketones and ethers in this fraction to; make it of great value as a thinner where aslight color is not objectionable.

Procedure with the under 200 C. fraction (method B) This method may be applied to the first fraction where it is desired to obtain either the aldehyde acids or the aldehydes in as high a state of purity as possible. In this case, instead of saponifying with caustic soda, I employ calcium hydroxide, as I have found that this reagent brings about very slight resinification of the aldehydic substances. In this procedure the fraction is boiled under an invert condenser with an excess of calcium hydroxide solution, starting .with five volumes of the oxidation product fraction and one volume of the lime water solution and adding more of the lime solution as the reaction proceeds.

, The calcium soaps may then be decomposed by a suitable mineral acid in the presence of alcohol, to form esters of the organic acids present; or the liberated acids may now be resinifled caustic soda by a treatment similar to that above recited under A" process.

Bythe lime saponification, a product of a good color is obtained from a non-saponifiable layer without further treatment. This method is particularly applicable where it is desired to isolate the aldehydes for any purpose. All that is neces-. sary is to agitate the non-saponifiable layer with a saturated or nearly saturated solution of sodium bisulphite, later removing and decomposing the aldehyde-bisulphite compound. Any ketones present are removed along with the aldehydes.

The non-aldehydic portion will .contain many oxidation derivatives, such as alcohols, ethers andpossibly bridge oxygen derivatives of the original hydrocarbons. I

Procedure with the 200 to 250? fraction (method A) When the saponiflcation is carried out as in the preceding A treatment with no further treatoil may, after the removal of the acids, be utilized as a furnace oil, and is of special advantage in gravity feed burners. On account of its containing oxygen compounds, this material is readily combustible. Tests have shown that the comdraft and gravity burner conditions.

still lower melting points.

bustion is clean and complete, leaving no carbon or tarry matters; whereas the ordinary kerosene hydrocarbon mixture in the same boiling range produces sooting and clogging under the same This fraction may be used alone as a furnace oil or it may be blended with ordinary hydrocarbons of either the same range or even of higher'boiling range,

since it acts as a kindling oil for the ordinary hydrocarbon and greatly minimizes the smoking and sooting thereof under burner conditions.

Where this non-saponifiable fraction is not used as a furnace oil, it may be readily handled by returning it to the oxidizing apparatus, either alone or mixed with fresh oil. Where this is done, I have found that the partially oxidized oil is always attacked and oxidizes more readily than fresh oil when subjected to the air-vapor catalytic Procedure with the'250 to 300 C. fraction This fraction wil1,in general, be handled the same as the 200' to 250 C. out, but the resin acids will have lower melting points and the nonsaponifiable oil will have a higher boiling range. The untreated resin acids should soften in the neighborhood of 145 C. The removal of aldehydes and ketones should in this case preferably be preceded by calcium hydroxide treatment, as before noted.

Procedure with the 300 to 350 fraction (method A) This method is carried out the same as 'in the preceding groups, and the resin acids will have For example, with the wax distillate gas oil product which I have described, resin acids were obtained from this out which, when untreated, softened at 132 C. and were completely melted at 138 C.- These resins were diss'olved almost completely (95%) 'in alcohol and were completely dissolved in benzol.

Procedure with the 300 to 350 0. fraction (method B) oxidizer or'may be used for lubrication where a thin oil is desired.

Procedure with the 300 to 350 c. fraction (method This method involves the sulphonation of the total 300 to 350 C. out. I prefer to carry out this sulphonatlon as follows: 5 volumes of the oxidized oil of this out are treated with one volume of fuming sulphuric acid (approximately lilZoleum) .by dropping the acid slowly into the oil with .violent agitation, keeping the tmpe'ratureb'elow 50 C. and continuing the agitation for three hours after all of the acid'is added; When the reaction mixture is allowed tostand for'from 48 to 72 hours, the excess sulphuric acid,.together with water and a considerable quantity of the sulphonated organic product, settles to the bottom}, The top oil layer here contains the sulphonated and other acids that are soluble in the oil. It is better to draw this off carefully from the sulphuric layer below and saponify by agita- J tion with hot causticsoda or sodium carbonate solution. If a solubleoil is desired, it is possible by careful addition of alkali to saponify the sul-.

phonated and other acids and leave a sufllcient amount of soda soap in the oil to completely emulsify it when water is added. A good plan here is to saponify to this point by heating the oil with dry caustic soda when the greater part of the soap remains in solution in the oil.

Instead of saponifying the acids in the top" oil by caustic soda or sodium carbonate,-as above, I may use calcium hydroxide and thus convert the whole top oil layer intoa grease.

I may saponify with caustic soda or sodium carbonate as above and remove the soda soaps by repeated washings, utilizing the separated soaps as cheap detergents.

The "sulphuric layer above referred to is 1 It froths readily and emulsifies oils more readily than do the ordinary commercial soaps.

Procedure with 350'to 400 0. fraction (method A) This method is that of isolating the resin acids as outlined for the preceding fractions. Here,

however, this is usually not advisable, as the resins from the foregoing wax distillate gas oil oxidation mixture were darker in color than those from the lighter fractions and showed a softening point of 62 C. and were completely melted at 66 C. Their solubility was almost identical with that of the resins from the preceding fraction.

Procedure with 350, to 400 0. fraction.

' (method B) There is present in this fraction an oxldation mixture of sufliciently high average molecular weight to show in the acids the characteristics of Procedure with 350 to 400 0. fraction' (method 0) This method relates to the sulphonation of the fraction and is carried out in a manner almost identical with that outlined for the third method of the preceding fraction. Here again it should be noted that the high average molecular weight of the acids and the non-saponiiiable oil imparts to the oxidation mixture the characteristics of the ordinary fatty acids and fatty oils. v

In all the foregoing outlines, I have considered those oxidation products of hydrocarbons which temperature and pressure, this being the mixture obtained at condensers in the ordinary operation of the catalytic vapor-phase oxidation.

' Procedure with scrubber product There is, however, another product which also consists of a mixture of oxidation compounds and which does not ordinarily condense with the products above noted, but is .usually carried onpast the condensers with the eiliuent gas stream.

If a scrubbing system be installed in series with the condensers and the scrubbing liquid consist of linfe water or a solution of, say, soda ash, I can almost completely-remove these low molecular weight bodies from the gas vapor efiluent. I have found these particular bodies to be most active toward the resiniflcation reaction, of any of the acids formed in the catalytic oxidation process. Because of this fact, it is preferable in most cases .to use lime water in the scrubbing system, as this is the mildest cheap alkali available. Even on warming the solution of these calcium soaps (since these calcium soaps are more soluble in water than those from any of the preceding oxidation products described) calcium resinates are obtained which become darker brown as the heating continues. The color of the resin acids liberated and the degree of resinification depend on the time during which the alkali or alkaline earth metal soaps are heated in contact with the free alkali or the free alkaline earth metal hydroxide. Where sodium carbonate or caustic soda is the alkali used in the scrubbing solution, the resiniflcation may be carried to the point of making brown resins that are infusible and insoluble in any of the ordinary solvents, such as alcohol,

benz ol, etc.

Where these soaps are in solution, I may bleach them by treating the solution with a stream of chlorine gas. Passage of the gas may be continued until enough acid has been formed to liberate the bleached resin acids. found that if dilute sulphuric acid be used to liberate the acids already resinified, chlorine may be used on the remaining acids in solution to resinify and finally precipitate the bleached resin acids formed.

Washing method of acid separation In addition to the foregoing procedures for the separation of the resin acids of the various fractions, it isv possible witheach fraction to separate these acids into two or more groups, each group having different properties, by the selective action of certain solvents. For example, as noted in the description of the products of. the first fraction, I have found that if the resins of a certain fraction be agitated with petroleum ether or gasoline, two groups of acids are obtained, one group being insoluble in petroleum ether or gasoline and having a much higher melting point than the original mixture of resins, and of course, a much higher melting point than the portion soluble in petroleum ether. or gasoline. I have found after much experimentation. that the application of the gasolinewash raises the melting point of the resins of a certain fraction which are not soluble in the H wash by from 20 to 30 or even 50 C. It is reving point to fall below C. Amounts as low as 5% of the gasoline-soluble acids will keep the melting point too low for many purposes, and yet the simple washing method above described I have also will result in a yield of from 90 to 95% of a resin mixture melting from 20 C. to 30 C. higheia,

By treating any of. the above resinified products from the oil fractions, preferably while in the form of their soluble soaps, (usually sodium or.

potassium soaps), with chlorine in the water solution, bleached resins of fine appearance can be obtained. Usually such resins, like practically all those above described, are soluble in alcohol or in benzol or in mixtures of these two solvents.

In all my processes of resinification, the property of the product obtained was determined by several factors, of which I believe the following to be the main ones:

(1) Chemical character of the hydrocarbons originally subjected to the air-vapor-catalyticoxidation; a

' (2) The particular fraction of the product from which the resins have been separated;

(3) The method of resinification. This is described in my copending application Serial No.-

520,715, for the renewal of. application Serial No. 395,942, filed July 13, 1920 and also in this application. Generally speaking, the milder the alkali used, the less will be the resinification. For example, it is possible in the case of the calcium soaps of low molecular weight acids to obtain suilicient resinification by the use of lime only, while if these acids be liberated from the calcium and be further resinified by caustic soda solution, I obtain resins practically ,infusible and insoluble. A convenient method of separating and resinifying the acids of a given reaction mixture is to carry out the saponification with a mixture of sodium carbonate and calcium hydroxide (slaked lime). I prefer to keep the calcium hydroxide in excess, for example, I may use from 8 to 10. grams molecular weights of calcium hydroxide to one g. mol. of sodium carbonate. This enables me to utilize the action of a dilute solution of caustic soda in saponification and to continuously remove the soaps formed, asinsoluble calcium soaps. The removal of these soaps from the sphere of the reaction hastens the saponiflcation of the remaining acids and acid compounds and anhydrides present in the reaction mixture.

Such a mixture may also be used as a scrubbing I liquid to aid in the further recovery ofthe vola- These resins are of higher melting point in a given fraction and more diflicultly soluble than the petroleum-ether soluble acids. Where the oxidation has been vigorous, the concentration of caustic used in saponification and resinification becomes of minor importance. In addition where color is an important factor in the resin produced,- I may bleach the product by taking the water solution of the sodium resinates and passing chlorine gas into the solution or by treating the solution with a solution of sodium hypochloride. Where chlorine is used, Imay proceed with the chlorine treatment until hydrochloric acid is formed in suflicient amount to liberate the bleached resin acids, without further mineral acid treatment. I may also pass chlorine into a suspension of the calcium resins, although this method is not as eifective as the sodium method above. Treating either the original fraction or the sodium soap with a solution of bleaching powder may also be used.

Where it is desired to improve certain physical properties of the resin acids, such as toughness and elasticity, I can accomplish this by taking any of the foregoing resin acids and forming their glycerine esters. This is usually carried out by heating the resin acid mixture with an excess of glycerine, usually aiding the esterification by the addition of a small percentage of sulphuric acid or by passing a stream of dry hydrochloric acid gas through the heated solution. After the esterification is complete, the excess glycerine is easily recovered by adding water to the cooled reaction mixture and the esterifled resin acids filtered oil and washed.

I claim:

1. In the treatment of partial oxidation products in the range from alcohols to organic acids and containing hydrocarbon derivatives other than acids, the steps consisting of separating from the same a plurality of fractions, each containing a material percentage of derivatives other than acids, and chemically treating at least one of said fractions.

2. In the treatment of a liquid partial oxidation product in the range from alcohols to organic acids and containing hydrocarbon derivatives other than acids, the steps consisting of separating from the same a fraction by distillation containing a material percentage of aliphatic deriv atives other than acids, then converting a portion of said fraction into resin acids and removing impurities from said acids.

3. In the treatment of a liquid partial oxidation product in the range from alcohols to organic acids and containing hydrocarbon derivatives other than acids, the steps consisting of separating from the same a fraction by distillation containing a material percentage of aliphatic derivatives other than acids, and then saponifying a portion of said fraction, separating the saponified from the unsaponified portion of said fraction, and bleaching the. saponified portion.

4. In the\treatment of a liquid partial oxidation product in the range from alcohols to organic acids and containing hydrocarbon derivatives other than acids, the steps consisting of separating from the samea fraction by distillation containing a material percentage of aliphatic derivatives other than acids, then saponifying a portion of said fraction with lime, and separating the saponified from the fraction.

5. In the treatment of a liquid partial oxidation product in the range from alcohols to organic acids and containing hydrocarbon derivatives other than acids, the steps consisting of separating from the same afraction by distillation containing a material percentage of aliphatic derivatlves other than acids, then saponifying a portion of said fraction with soda and lime, and separating the saponified from the unsaponified portion of said fraction. I

6. In the treatment of partial oxidation products of hydrocarbons, the steps consisting of resiniiying at least a portion thereof, and then washing out of said resinified material the lower-meltingpoint portions thereof.

7. In the treatment of liquid partial oxidation mixtures in the range from alcohols to aldehyde fatty acids, the steps consisting of vacuum distilling the same into fractions of diiferent average molecular weight, and then chemically treating unsaponified portion of said at least one of the fractions to form chemical compounds of portions of said fractions, and separating said compounds.

8. In the treatment of liquid partial oxidation mixtures in the range from alcohols to aldehyde fatty acids. the steps consisting of steam vacuum distilling the same into fractions of difierent average molecular weight, and then chemically treating at least one of the fractions to form chemical compounds of portions of said fractions, and separating said compounds.

i 9. I In the treatment of a. partial oxidation prodnot having hydrocarbons which already contain artificially-introduced chemically-combined oxygen to difierent degrees of oxidation, and which contain like bodies of different molecular weights,

the steps consisting of fractionating the same into liquid fractions of different average molecular weights and treating the lighter fractions with a resinifying agent.

acids, and sulphonating aheavier fraction whose major portionconsists of bodies boiling overa 11. In the treatment of a mixture of oxygen 30 derivatives of hydrocarbons inwhich aliphatic 10. In the treatment of partial oxidation prod-V hydrocarbons predominate containing alcohols and having a boiling point above 300 C., the step consisting of sulphonating the same.

12. In the treatment of a mixture of oxygen derivatives of hydrocarbons in which aliphatic hydrocarbons predominate containing alcohols and having aboiling point above 300 C., the step consisting of sulphonating. the same and then saponifying.

13. As a new composition of matter, a mixture of sulphonated oxygen derivatives of hydrocarbons in which aliphatic hydrocarbons predominate having a boiling point above 300 C. j

14;. As a new composition of matter, a detergent containing essentially a sulfonated and saponificd mixture of oxygen derivatives of hydrocarbons in which aliphatic hydrocarbons predominate having a boiling point above 300 C.,

15. As a new composition of matter, a sulpho nated and saponified fraction of a mixture of oxygen derivatives of hydrocarbons in'which aliphatic hydrocarbons predominate having a boiling point above 300 C.

16. As a new composition of matter, the reac- 'tion product of sulphuric acid and a fraction boil ing over 300 C of a mixture of oxygen derivatives of hydrocarbons in which aliphatic hydrocarbons 

